U.S. patent application number 17/611057 was filed with the patent office on 2022-08-11 for diol compound, polycarbonate, and preparation method thereof.
The applicant listed for this patent is LG CHEM, LTD.. Invention is credited to Mooho HONG, Daehyeon HWANG, Young Young HWANG, Dayoung LEE, Ki Jae LEE, Youngwook SON.
Application Number | 20220251056 17/611057 |
Document ID | / |
Family ID | |
Filed Date | 2022-08-11 |
United States Patent
Application |
20220251056 |
Kind Code |
A1 |
LEE; Dayoung ; et
al. |
August 11, 2022 |
DIOL COMPOUND, POLYCARBONATE, AND PREPARATION METHOD THEREOF
Abstract
Provided are a diol compound which may be used to prepare a
polycarbonate having excellent weather resistance, hardness, heat
resistance, transparency, impact resistance, etc. while having
excellent mechanical properties, a polycarbonate prepared by using
the same, and a preparation method thereof.
Inventors: |
LEE; Dayoung; (Daejeon,
KR) ; LEE; Ki Jae; (Daejeon, KR) ; HONG;
Mooho; (Daejeon, KR) ; HWANG; Young Young;
(Daejeon, KR) ; SON; Youngwook; (Daejeon, KR)
; HWANG; Daehyeon; (Daejeon, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
LG CHEM, LTD. |
Seoul |
|
KR |
|
|
Appl. No.: |
17/611057 |
Filed: |
September 3, 2020 |
PCT Filed: |
September 3, 2020 |
PCT NO: |
PCT/KR2020/011857 |
371 Date: |
November 12, 2021 |
International
Class: |
C07D 307/68 20060101
C07D307/68; C07D 333/38 20060101 C07D333/38; C08G 64/24 20060101
C08G064/24; C08G 64/08 20060101 C08G064/08; C08G 63/64 20060101
C08G063/64; C08G 64/30 20060101 C08G064/30 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 5, 2019 |
KR |
10-2019-0110305 |
Sep 2, 2020 |
KR |
10-2020-0111774 |
Claims
1. A diol compound represented by Chemical Formula 1: ##STR00021##
wherein, in Chemical Formula 1, X is --O-- or --S--, R is
C.sub.6-60 arylene unsubstituted or substituted with C.sub.1-10
alkyl, and n is an integer of 1 to 100.
2. The diol compound of claim 1, wherein the diol compound
represented by Chemical Formula 1 is one of the compounds
represented by Chemical Formula 1-1 to Chemical Formula 1-3:
##STR00022## wherein, in Chemical Formulae 1-1 to 1-3, X, R, and n
are the same as defined in Chemical Formula 1.
3. A polycarbonate comprising: a repeating unit derived from a diol
compound represented by Chemical Formula 1; a repeating unit
derived from a compound represented by Chemical Formula 2; and a
carbonate precursor-derived repeating unit: ##STR00023## wherein,
in Chemical Formula 1, X is --O-- or --S--, R is C.sub.6-60 arylene
unsubstituted or substituted with C.sub.1-10 alkyl, and n is an
integer of 1 to 100, ##STR00024## wherein, in Chemical Formula 2,
R.sub.1 to R.sub.4 are each independently hydrogen, C.sub.1-10
alkyl, C.sub.1-10 alkoxy, or halogen, Z is C.sub.1-10 alkylene
unsubstituted or substituted with phenyl, C.sub.3-15 cycloalkylene
unsubstituted or substituted with C.sub.1-10 alkyl, O, S, SO,
SO.sub.2, or CO.
4. The polycarbonate of claim 3, wherein the diol compound
represented by Chemical Formula 1 is one of the compounds
represented by Chemical Formula 1-1 to Chemical Formula 1-3:
##STR00025## wherein, in Chemical Formulae 1-1 to 1-3, X, R, and n
are the same as defined in Chemical Formula 1.
5. The polycarbonate of claim 3, wherein R.sub.1 to R.sub.4 are
each independently hydrogen or C.sub.1-4 alkyl.
6. The polycarbonate of claim 3, wherein a weight ratio of a
repeating unit derived from the compound represented by Chemical
Formula 1 to a repeating unit derived from the compound represented
by Chemical Formula 2 is 5:95 to 50:50.
7. The polycarbonate of claim 3, comprising a repeating unit
represented by Chemical Formula 3: ##STR00026## wherein, in
Chemical Formula 3, X, R, and n are the same as defined in Chemical
Formula 1.
8. The polycarbonate of claim 3, comprising a repeating unit
represented by Chemical Formula 4: ##STR00027## wherein, in
Chemical Formula 4, R.sub.1 to R.sub.4, and Z are the same as
defined in Chemical Formula 2.
9. The polycarbonate of claim 3, wherein pencil hardness of the
polycarbonate is B or HB, as measured under a load of 1 kg at an
angle of 45 degree in accordance with ASTM D3363.
10. The polycarbonate of claim 3, wherein weather resistance
(.DELTA.E value) measured according to Equation 1 is 1 to 11:
.DELTA.E= {square root over
(((L'-L).sup.2+(a'-a).sup.2+(b'-b).sup.2))} [Equation 1] wherein,
in Equation 1, L, a, and b are values of a specimen having a
thickness of 1/8 inch, measured in accordance with ASTM D7869
method, and L', a' and b' are values measured again after leaving
the corresponding specimen under 2250 hr weather resistance.
11. A method of preparing a polycarbonate, the method comprising a
step of: polymerizing a composition including a diol compound
represented by Chemical Formula 1, an aromatic diol compound
represented by Chemical Formula 2, and a carbonate precursor:
##STR00028## wherein, in Chemical Formula 1, X is --O-- or --S--, R
is C.sub.6-60 arylene unsubstituted or substituted with C.sub.1-10
alkyl, and n is an integer of 1 to 100, ##STR00029## wherein, in
Chemical Formula 2, R.sub.1 to R.sub.4 are each independently
hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen, and Z is
C.sub.1-10 alkylene unsubstituted or substituted with phenyl,
C.sub.3-15 cycloalkylene unsubstituted or substituted with
C.sub.1-10 alkyl, O, S, SO, SO.sub.2, or CO.
12. The method of claim 11, wherein the diol compound represented
by Chemical Formula 1 is one of the compounds represented by
Chemical Formula 1-1 to Chemical Formula 1-3: ##STR00030## wherein,
in Chemical Formulae 1-1 to 1-3, X, R, and n are the same as
defined in Chemical Formula 1.
13. The method of claim 11, wherein the aromatic diol compound
represented by Chemical Formula 2 is one or more compounds selected
from the group consisting of bis(4-hydroxyphenyl)methane,
bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone,
bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide,
bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane,
2,2-bis(4-hydroxyphenyl)propane (bisphenol A),
2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane
(bisphenol Z), 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane,
2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane,
2,2-bis(4-hydroxy-3-bromophenyl)propane,
2,2-bis(4-hydroxy-3-chlorophenyl)propane,
2,2-bis(4-hydroxy-3-methylphenyl)propane,
2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, and
1,1-bis(4-hydroxyphenyl)-1-phenylethane.
14. A molded article comprising the polycarbonate of claim 3.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application is a National Phase entry pursuant
to 35 U.S.C. .sctn. 371 of International Application No.
PCT/KR2020/011857, filed on Sep. 3, 2020, and claims priority to
and the benefit of Korean Patent Application Nos. 10-2019-0110305
and 10-2020-0111774, filed on Sep. 5, 2019 and Sep. 2, 2020,
respectively, the disclosures of which are hereby incorporated
herein by reference in their entirety for all purposes as if fully
set forth herein.
TECHNICAL FIELD
[0002] The present invention relates to a diol compound, a
polycarbonate, and a preparation method thereof. More specifically,
the present invention relates to a diol compound which may be used
to prepare a novel structure of a polycarbonate having improved
weather resistance, hardness, heat resistance, impact resistance,
etc. while having excellent mechanical properties, a polycarbonate
prepared by using the same, and a preparation method thereof.
BACKGROUND
[0003] Polycarbonate resins have excellent impact strength,
dimensional stability, heat resistance, transparency, etc., and
thus the polycarbonate resins are polymeric materials having
application in a wide range of uses, such as exterior materials of
electrical and electronic products, automobile parts, building
materials, optical components, etc.
[0004] As the application fields of these polycarbonate resins have
recently expanded, such as being applied to glass and lenses, there
is a need for the development of a novel structure of polycarbonate
with improved weather resistance and refractive index while
maintaining intrinsic properties of the polycarbonate resins.
[0005] Accordingly, studies have been attempted to obtain desired
physical properties by copolymerizing two or more kinds of aromatic
diols having different structures to introduce units having
different structures into the main chain of polycarbonate. However,
most technologies have limitations in that production costs are
high, and when chemical resistance or impact strength increases,
transparency decreases, and on the contrary, when the transparency
increases, the chemical resistance or impact strength
decreases.
[0006] Accordingly, there is still a need for research and
development on a novel structure of polycarbonate, which has
excellent weather resistance, heat resistance, transparency,
hardness, and impact resistance while having excellent mechanical
properties such as hardness, etc.
SUMMARY OF THE INVENTION
[0007] There is provided a diol compound which can be used to
prepare a polycarbonate having improved weather resistance,
hardness, heat resistance, and impact resistance while having
excellent mechanical properties, a polycarbonate prepared by using
the same, and a preparation method thereof.
[0008] There is provided a diol compound represented by Chemical
Formula 1.
[0009] Further, there is provided a polycarbonate including the
diol compound represented by Chemical Formula 1, a compound
represented by Chemical Formula 2, and a carbonate
precursor-derived repeating unit.
[0010] Further, there is provided a method of preparing a
polycarbonate, the method including the step of polymerizing a
composition including the diol compound represented by Chemical
Formula 1, the compound represented by Chemical Formula 2, and the
carbonate precursor.
[0011] Hereinafter, a diol compound, a polycarbonate, and a
preparation method thereof according to specific embodiments of the
present invention will be described in more detail.
[0012] According to one specific embodiment of the present
invention, provided is a diol compound represented by the following
Chemical Formula 1:
##STR00001##
[0013] in Chemical Formula 1,
[0014] X is --O-- or --S--,
[0015] R is C.sub.6-60 arylene unsubstituted or substituted with
C.sub.1-10 alkyl, and
[0016] n is an integer of 1 to 100.
[0017] The diol compound represented by Chemical Formula 1 has a
novel modified structure including a 5-membered hetero ring group
and carboxylates in the middle thereof and hydroxybenzoates at both
ends thereof, and can function as a diol monomer compound in the
polymerization of polycarbonate, and can have excellent impact
resistance, transparency, heat resistance, etc., which are
intrinsic properties of existing polycarbonate, while also
exhibiting excellent weather resistance and hardness
properties.
[0018] More specifically, the compound represented by Chemical
Formula 1 has a structure in which hydroxybenzoates and a
5-membered hetero ring group are connected to each other via the
carboxylate groups, and can exhibit excellent hardness, weather
resistance, etc., as compared with existing polycarbonate, due to a
structural change by fries-rearrangement of ester groups of the
hydroxybenzoates, and the 5-membered hetero ring group. In
addition, the effects of improving weather resistance and hardness
of the polycarbonate can be further increased according to the
number of (n) of the repeating units, the kind of hetero atom (X),
and the ester linkage position of hydroxybenzoate, and different
structures of the substituent R included in the structure of
Chemical Formula 1.
[0019] As used herein, the alkyl group can be a linear or branched
alkyl group having 1 to 10 carbon atoms or 1 to 5 carbon atoms.
Specific examples of the alkyl group can include methyl, ethyl,
propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl,
sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl,
isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl,
2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl,
heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl,
1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl,
2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl,
2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but are not
limited thereto.
[0020] As used herein, the cycloalkylene can be a monocyclic,
polycyclic, or condensed cycloalkylene group having 3 to 20 carbon
atoms or 3 to 15 carbon atoms. Specific examples of the
cycloalkylene group include cyclopropane, cyclobutane,
cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane,
etc., but are not limited thereto.
[0021] The arylene having 6 to 60 carbon atoms can be a monocyclic
arylene or a polycyclic arylene. Specifically, the arylene having 6
to 60 carbon atoms can be a monocyclic or polycyclic arylene having
6 to 30 carbon atoms; or monocyclic or polycyclic arylene having 6
to 20 carbon atoms. More specifically, the arylene having 6 to 60
carbon atoms can include, as the monocyclic arylene, divalent
residues derived from aromatic hydrocarbons, such as benzene,
biphenyl, diphenylmethane, diphenylpropane, terphenyl, etc., and as
the polycyclic arylene, divalent residues derived from aromatic
hydrocarbons, such as naphthalene, anthracene, phenanthrene,
triphenylene, pyrene, perylene, chrysene, fluorene, etc., but is
not limited thereto. Further, the arylene having 6 to 60 carbon
atoms can be substituted or unsubstituted with an alkyl group
having 1 to 10 carbon atoms.
[0022] As used herein, the fluorene can be substituted, and two
substituents can be connected to each other to form a spiro
structure. When the fluorene is substituted, it can be
##STR00002##
etc., but is not limited thereto.
[0023] As used herein, the heterocycloalkylene means that one or
more of carbon atoms constituting the cycloalkylene group are
substituted with one or more hetero atoms selected from the group
consisting of N, O, P, Si, S, and combinations thereof.
[0024] According to one exemplary embodiment of the present
invention, X in Chemical Formula 1 can be oxygen (--O--) or sulfur
(--S--).
[0025] Further, in Chemical Formula 1, R can be
##STR00003##
[0026] According to one exemplary embodiment of the present
invention, considering the effect on the improvement of weather
resistance and hardness of polycarbonate, n of Chemical Formula 1
can be an integer of 1 or more, or 2 or more, or 3 or more, or 5 or
more, or 10 or more, or 14 or more, and 100 or less, or 50 or less,
or 30 or less, or 20 or less, or 10 or less. Preferably, n of
Chemical Formula 1 can be 2 to 10. When n is excessively large,
solubility of the compound of Chemical Formula 1 is lowered, and
thus productivity or processability of the polycarbonate may be
poor.
[0027] According to one exemplary embodiment of the present
invention, the diol compound represented by Chemical Formula 1 can
be represented by the following Chemical Formula 1-1 to Chemical
Formula 1-3:
##STR00004##
[0028] in Chemical Formulae 1-1 to 1-3,
[0029] X, R, and n are the same as defined in Chemical Formula
1.
[0030] According to one exemplary embodiment of the present
invention, a weight average molecular weight (Mw) of the compound
of Chemical Formula 1 can be appropriately controlled according to
the purpose and use, and can be 500 g/mol or more, or 1,000 g/mol
or more, or 1,500 g/mol or more, and 10,000 g/mol or less, or 5,000
g/mol or less, or 3,000 g/mol or less. In this regard, the weight
average molecular weight can be obtained in terms of standard
polystyrene (PS Standard) conversion value by gel permeation
chromatography (GPC).
[0031] According to one exemplary embodiment of the present
invention, the compound of Chemical Formula 1 can be used alone or
in combination with another diol compound upon polymerization of
the polycarbonate.
[0032] The compound of Chemical Formula 1 can be prepared according
to a known method of preparing organic compounds, and for example,
can be prepared according to the following Reaction Scheme 1. The
method of preparing the compound of Chemical Formula 1 will be
described in detail in Examples below.
##STR00005##
[0033] in Reaction Scheme 1, X, R, and n are the same as defined in
Chemical Formula 1.
[0034] According to another exemplary embodiment of the present
invention, provided is a polycarbonate including a diol compound
represented by the following Chemical Formula 1, a compound
represented by the following Chemical Formula 2, and a carbonate
precursor-derived repeating unit:
##STR00006##
[0035] in Chemical Formula 1,
[0036] X is --O-- or --S--,
[0037] R is C.sub.6-60 arylene unsubstituted or substituted with
C.sub.1-10 alkyl, and
[0038] n is an integer of 1 to 100,
##STR00007##
[0039] in Chemical Formula 2,
[0040] R.sub.1 to R.sub.4 are each independently hydrogen,
C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen,
[0041] Z is C.sub.1-10 alkylene unsubstituted or substituted with
phenyl, C.sub.3-15 cycloalkylene unsubstituted or substituted with
C.sub.1-10 alkyl, O, S, SO, SO.sub.2, or CO.
[0042] Description of Chemical Formula 1 and specific exemplary
compounds thereof are as described above.
[0043] According to one exemplary embodiment of the present
invention, the compound represented by Chemical Formula 2 can be
represented by the following Chemical Formula 2-1:
##STR00008##
[0044] The polycarbonate of the present invention can be composed
of only the repeating units derived from the compounds represented
by Chemical Formula 1 and Chemical Formula 2, or can further
include a repeating unit derived from another aromatic diol
compound in addition thereto.
[0045] In Chemical Formula 2, R.sub.1 to R.sub.4 can be each
independently hydrogen or C.sub.1-4 alkyl. Alternatively, R.sub.1
to R.sub.4 can be each independently hydrogen, methyl, chloro, or
bromo.
[0046] Further, in Chemical Formula 2, Z is each independently
linear or branched C.sub.1-10 alkylene unsubstituted or substituted
with phenyl, and more preferably, methylene, ethane-1,1-diyl,
propane-2,2-diyl, butane-2,2-diyl, 1-phenylethane-1,1-diyl, or
diphenylmethylene.
[0047] The polycarbonate according to one exemplary embodiment of
the present invention can include a repeating unit represented by
the following Chemical Formula 3:
##STR00009##
[0048] in Chemical Formula 3,
[0049] X, R, and n are the same as defined in Chemical Formula
1.
[0050] Further, the polycarbonate according to one exemplary
embodiment of the present invention can include a repeating unit
represented by the following Chemical Formula 4:
##STR00010##
[0051] in Chemical Formula 4,
[0052] R.sub.1 to R.sub.4, and Z are the same as defined in
Chemical Formula 2.
[0053] The repeating unit derived from Chemical Formula 1 is
characterized by having excellent hardness and weather resistance,
and the repeating unit derived from Chemical Formula 2 is
characterized by having excellent transparency, heat resistance,
and impact resistance, and a weight ratio of the repeating units
derived from Chemical Formulae 1 and 2 can be controlled to prepare
a polycarbonate having desired physical properties.
[0054] When the polycarbonate of the present invention includes the
repeating unit derived from Chemical Formula 2 in addition to the
repeating unit derived from Chemical Formula 1, a weight ratio
thereof is not particularly limited, but for example, the weight
ratio of the repeating unit derived from Chemical Formula 1 and the
repeating unit derived from Chemical Formula 2 can be 5:95 to
50:50. In one specific exemplary embodiment, the weight ratio of
the repeating unit derived from Chemical Formula 1 and the
repeating unit derived from Chemical Formula 2 can be 5:95 to
50:50, or 10:90 to 40:60, or 10:90 to 30:70. When the weight ratio
of the Chemical Formula 1 is too low, the polycarbonate may have
insufficient hardness and weather resistance. On the contrary, when
the weight ratio of the Chemical Formula 1 is too high,
transparency or impact strength of the polycarbonate may decrease,
or reactivity may decrease, and thus productivity of the
polycarbonate may be decreased.
[0055] A weight average molecular weight (Mw) of the polycarbonate
can be appropriately controlled according to the purpose and use,
and can be 15,000 g/mol or more, or 20,000 g/mol or more, or 28,000
g/mol or more, and 70,000 g/mol or less, or 60,000 g/mol or less,
or 50,000 g/mol or less, or 48,000 g/mol or less, or 47,000 g/mol
or less. In this regard, the weight average molecular weight can be
obtained in terms of standard polystyrene (PS Standard) conversion
value by gel permeation chromatography (GPC).
[0056] Further, pencil hardness of the polycarbonate can exhibit
high hardness of B or HB, as measured under a load of 1 kg at an
angle of 45 degree in accordance with ASTM D3363.
[0057] Further, the polycarbonate of the present invention can have
weather resistance (.DELTA.E) of 11 or less, or 10 or less, or 9 or
less, or 8 or less, or 7 or less, wherein the weather resistance
(.DELTA.E) is calculated from L', a' and b' values which are
measured after measuring L, a, and b values in accordance with ASTM
D7869, and then leaving the corresponding specimen under 2250 hr
weather resistance condition using a Weather-Ometer.RTM.
instrument. It is more preferred that the weather resistance is
lower, and thus its lower limit is not particularly limited, but
can be, for example, 1 or more, or 3 or more, or 4 or more.
[0058] Meanwhile, according to still another specific embodiment of
the present invention, provided is a method of preparing the
polycarbonate, the method including the step of polymerizing a
composition including a compound represented by the following
Chemical Formula 1, an aromatic diol compound represented by the
following Chemical Formula 2, and a carbonate precursor:
##STR00011##
[0059] in Chemical Formula 1,
[0060] X is --O-- or --S--,
[0061] R is C.sub.6-60 arylene unsubstituted or substituted with
C.sub.1-10 alkyl, and
[0062] n is an integer of 1 to 100,
##STR00012##
[0063] in Chemical Formula 2,
[0064] R.sub.1 to R.sub.4 are each independently hydrogen,
C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen,
[0065] Z is C.sub.1-10 alkylene unsubstituted or substituted with
phenyl, C.sub.3-15 cycloalkylene unsubstituted or substituted with
C.sub.1-10 alkyl, O, S, SO, SO.sub.2, or CO.
[0066] Description of Chemical Formula 1 and specific exemplary
compounds thereof are as described above.
[0067] Specific examples of the aromatic diol compound represented
by Chemical Formula 2 can include one or more compounds selected
from the group consisting of bis(4-hydroxyphenyl)methane,
bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone,
bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide,
bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane,
2,2-bis(4-hydroxyphenyl)propane (bisphenol A),
2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane
(bisphenol Z), 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane,
2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane,
2,2-bis(4-hydroxy-3-bromophenyl)propane,
2,2-bis(4-hydroxy-3-chlorophenyl)propane,
2,2-bis(4-hydroxy-3-methylphenyl)propane,
2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, and
1,1-bis(4-hydroxyphenyl)-1-phenylethane.
[0068] Further, the carbonate precursor functions to connect the
compound represented by Chemical Formula 1 and the compound
represented by Chemical Formula 2, and specific examples thereof
can include phosgene, triphosgene, diphosgene, bromophosgene,
dimethyl carbonate, diethyl carbonate, dibutyl carbonate,
dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate,
bis(chlorophenyl) carbonate, m-cresyl carbonate,
dinaphthylcarbonate, bis(diphenyl) carbonate, or
bishaloformate.
[0069] According to one specific embodiment, the method of
polymerizing the polycarbonate using the composition including the
aromatic diol compound represented by Chemical Formula 2 and the
carbonate precursor in addition to the compound represented by
Chemical Formula 1 can be used to perform a polymerization process
at once on the composition including the above three precursor
compounds.
[0070] In this regard, the compound represented by Chemical Formula
1 can be used in an amount of 1% by weight or more, 2% by weight or
more, or 3% by weight or more, and 15% by weight or less, 12% by
weight or less, or 10% by weight or less, with respect to 100% by
weight of the composition.
[0071] Further, the aromatic diol compound represented by Chemical
Formula 2 can be used in an amount of 40% by weight or more, 50% by
weight or more, or 55% by weight or more, and 80% by weight or
less, 75% by weight or less, or 70% by weight or less with respect
to 100% by weight of the composition.
[0072] Further, the carbonate precursor can be used in an amount of
10% by weight or more, 15% by weight or more, or 20% by weight or
more, and 50% by weight or less, 40% by weight or less, or 35% by
weight or less with respect to 100% by weight of the
composition.
[0073] In this regard, the polymerization can be performed by any
method of interfacial polymerization or melt polymerization.
[0074] During the interfacial polymerization, it is preferred that
the polymerization temperature is 0.degree. C. to 40.degree. C.,
and the reaction time is 10 min to 5 hr. Further, during the
reaction, pH is preferably maintained at 9 or more, or 11 or
more.
[0075] The solvent that can be used in the polymerization is not
particularly limited as long as it is a solvent used in the art for
the polymerization of polycarbonate. For example, halogenated
hydrocarbons such as methylene chloride, chlorobenzene, etc. can be
used.
[0076] In addition, the polymerization is preferably carried out in
the presence of an acid binder, and as the acid binder, an alkali
metal hydroxide such as sodium hydroxide, potassium hydroxide,
etc., or an amine compound such as pyridine, etc. can be used.
[0077] Further, the polymerization is preferably performed in the
presence of a molecular weight controller in order to control the
molecular weight of polycarbonate during polymerization. As the
molecular weight controller, C.sub.1-20 alkylphenol can be used.
Specific examples thereof can include p-tert-butylphenol,
p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol,
hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, or
triacontylphenol. The molecular weight controller can be injected
before initiation of the polymerization, during initiation of the
polymerization, or after initiation of the polymerization. The
molecular weight controller can be used in an amount of 0.01 part
by weight to 10 parts by weight, preferably 0.1 part by weight to 6
parts by weight, based on 100 parts by weight of the aromatic diol
compound. Within this range, a desired molecular weight can be
obtained.
[0078] To promote the polymerization reaction, a reaction promoter,
for example, a tertiary amine compound such as triethylamine,
tetra-n-butylammoniumbromide, tetra-n-butylphosphoniumbromide,
etc., a quaternary ammonium compound, a quaternary phosphonium
compound can be further used.
[0079] According to still another specific embodiment of the
present invention, provided is a molded article manufactured by
using the polycarbonate. As described above, the polycarbonate
including the repeating unit derived from the compound represented
by Chemical Formula 1 can have excellent mechanical properties
while also having improved weather resistance, heat resistance, and
transparency. Therefore, the molded article can be applied to a
variety of fields, as compared with molded articles manufactured by
using the existing polycarbonate. Further, the weight ratio of the
repeating units derived from the compounds represented by Chemical
Formulae 1 and 2 can be controlled to prepare a polycarbonate
having desired physical properties.
[0080] The molded article can further include, if necessary, one or
more selected from the group consisting of an anti-oxidant, a
plasticizer, an antistatic agent, a nucleating agent, a flame
retardant, a lubricant, an impact modifier, an optical brightener,
an ultraviolet absorber, a pigment, and a dye, in addition to the
polycarbonate according to the present invention.
[0081] A method of manufacturing the molded article can include,
for example, the steps of mixing well the polycarbonate of the
present invention and other additive using a mixer,
extrusion-molding the mixture using an extruder to prepare a
pellet, drying the pellet, and then injecting the pellet using an
injection molding machine.
[0082] According to the present invention, provided are a novel
structure of a polycarbonate having improved weather resistance,
heat resistance, impact resistance, and hardness while having
excellent mechanical properties, and a preparation method
thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0083] FIG. 1 shows a 1H-NMR graph of a compound prepared in
Example 1;
[0084] FIG. 2 shows a 1H-NMR graph of a copolycarbonate prepared in
Example 1;
[0085] FIG. 3 shows a 1H-NMR graph of a compound prepared in
Example 2;
[0086] FIG. 4 shows a 1H-NMR graph of a copolycarbonate prepared in
Example 2;
[0087] FIG. 5 shows a 1H-NMR graph of a compound prepared in
Example 7;
[0088] FIG. 6 shows a 1H-NMR graph of a copolycarbonate prepared in
Example 7;
[0089] FIG. 7 shows a 1H-NMR graph of a compound prepared in
Example 8; and
[0090] FIG. 8 shows a 1H-NMR graph of a copolycarbonate prepared in
Example 8.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0091] The present invention will be described in more detail with
reference to the following exemplary embodiments. However, the
following exemplary embodiments are for illustrative purposes only,
and the scope of the present invention is not intended to be
limited by the following exemplary embodiments.
EXAMPLE
Example 1
[0092] (1) Preparation of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate
##STR00013##
[0093] Furan-2,5-dicarboxylic acid (8 g) was placed in a 250-mL
round bottom flask, dissolved in an MC solvent, and then oxalyl
chloride (14.31 g) and DMF (0.3 mL) were added dropwise at room
temperature, followed by stirring at room temperature for about 4
hours. When the reaction product became transparent, the solvent
was removed using a rotary evaporator to obtain a chlorinated solid
compound.
[0094] Thereafter, 4-hydroxybenzoic acid (21.23 g) was placed in a
500-mL round bottom flask, and dissolved in a 2 M NaOH aqueous
solution (105 mL). A solution obtained by dissolving the previously
obtained solid compound in tetrachloroethane solvent was added
dropwise to the reaction flask for 1 hour using a dropping funnel.
Thereafter, the mixture was further stirred for about 4 hours, and
the reaction was terminated using a hydrochloric acid solution
(35%). The resulting white solid was obtained through filtration
under reduced pressure and washed with water and methaneol during
filtration. The obtained solid was dried overnight in an oven at
60.degree. C., and recrystallized several times with acetone to
obtain a white dicarboxylic acid intermediate with a purity of
98%.
[0095] The dicarboxylic acid intermediate (10 g) was placed in a
250-mL round bottom flask, dissolved in an MC solvent, and oxalyl
chloride (9.64 g) and DMF (0.2 g) were added dropwise at room
temperature, followed by stirring at room temperature for about 4
hours. When the reaction product became transparent, the solvent
was removed using a rotary evaporator to obtain a chlorinated solid
compound.
[0096] In a separate 250-mL round flask, bisphenol A (11.81 g) was
stirred in pyridine (7.98 g) and MC solvent. The previously
completed compound without a separate purification process was
slowly added to the bisphenol A solution prepared in the flask.
After the addition, the reaction was allowed overnight at room
temperature. After the reaction was completed, 1N--HCl was used to
terminate the reaction, and after washing with Water/MC three
times, the residual moisture in the organic layer was removed using
MgSO.sub.4, and the organic solvent was removed using a rotary
evaporator. A yellow liquid final compound with viscosity (weight
average molecular weight: 4,900 g/mol, n=8-9) was obtained in a
final yield of 79%.
[0097] .sup.1H-NMR (DMSO-d.sub.6) of the compound is shown in FIG.
1.
[0098] (2) Preparation of Polycarbonate Resin
[0099] 620 g of water, 112.46 g of bisphenol A, 14.09 g of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate prepared in (1), 102.5 g of 40% by weight
of NaOH, and 200 ml of MeCl.sub.2 were added to a 2-L main reactor
equipped with a nitrogen purge device and a condenser and enabling
maintenance at room temperature using a circulator, followed by
stirring for several minutes.
[0100] Nitrogen purging was stopped, 62.8 g of triphosgene and 120
ml of MeCl.sub.2 were placed in a 1-L round bottom flask,
triphosgene was dissolved therein, and the dissolved triphosgene
solution was slowly added to the main reactor. After the addition
was completed, 2.7 g of PTBP (p-tert-butylphenol) was added and
stirred for 10 min. After stirring was completed, 99.8 g of 40% by
weight of a NaOH aqueous solution was added, and 1.5 ml of TEA as a
coupling agent was added. At this time, reaction pH was maintained
at 11 to 13. After the reaction solution was allowed to stand for a
time for sufficient reaction, pH was decreased to 3-4 by addition
of HCl to complete the reaction. Then, stirring was stopped, the
polymer layer was separated from the aqueous layer, the aqueous
layer was removed, and the residue was washed with pure H.sub.2O
again, and this process was repeated a total of 3 to 5 times.
[0101] After the washing was completely carried out, only the
polymer layer was extracted, and polymer crystals were obtained by
re-precipitation using a non-solvent of methanol, H.sub.2O, etc. In
this regard, a weight average molecular weight of the prepared
polycarbonate was 48,000 g/mol, in terms of PS standard.
[0102] Further, the results of NMR analysis confirmed that the
repeating unit derived from the compound (1) was included in an
amount of 10 wt %, based on the weight of the total repeating
units.
[0103] .sup.1H-NMR (CDCl.sub.3-d.sub.1) of the compound is shown in
FIG. 2.
Example 2
[0104] (1) Preparation of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
thiophene-2,5-dicarboxylate
##STR00014##
[0105] Synthesis was performed in the same manner as in (1) of
Examples 1, except that 8.82 g of thiophene-2,5-dicarboxylic acid
was used instead of 2,5-Furandicarboxylic acid of Example 1.
[0106] The final compound,
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
thiophene-2,5-dicarboxylate (weight average molecular weight: 3,500
g/mol, n=5.about.6) was obtained in a final yield of 72%.
[0107] .sup.1H-NMR (DMSO-d.sub.6) of the compound is shown in FIG.
3.
[0108] (2) Preparation of Polycarbonate Resin
[0109] A polycarbonate was prepared in the same manner as in the
method of preparing a polycarbonate of Example 1, except that 14.03
g of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
thiophene-2,5-dicarboxylate prepared in (1) was used instead of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate of Example 1, and 112.55 g of bisphenol-A
was used. In this regard, a weight average molecular weight of the
prepared polycarbonate was 46,400 g/mol, in terms of PS standard.
Further, the results of NMR analysis confirmed that the repeating
unit derived from the compound (1) was included in an amount of 10
wt %, based on the weight of the total repeating units.
[0110] .sup.1H-NMR (CDCl.sub.3-d.sub.1) of the compound is shown in
FIG. 4.
Example 3
[0111] (1) Preparation of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate
##STR00015##
[0112] The same compound as in (1) of Example 1 was used.
[0113] (2) Preparation of Polycarbonate Resin
[0114] A polycarbonate was prepared in the same manner as in the
method of preparing a polycarbonate of Example 1, except that 6.74
g of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate of Example 1 and 114.55 g of bisphenol-A
were used. In this regard, a weight average molecular weight of the
prepared polycarbonate was 45,200 g/mol, in terms of PS standard.
Further, the results of NMR analysis confirmed that the repeating
unit derived from the compound (1) was included in an amount of 5
wt %, based on the weight of the total repeating units.
Example 4
[0115] (1) Preparation of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
thiophene-2,5-dicarboxylate
##STR00016##
[0116] The same compound as in (1) of Example 2 was used.
[0117] (2) Preparation of Polycarbonate Resin
[0118] A polycarbonate was prepared in the same manner as in the
method of preparing a polycarbonate of Example 1, except that 6.75
g of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
thiophene-2,5-dicarboxylate of Example 2 was used instead of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate and 114.59 g of bisphenol-A was used. In
this regard, a weight average molecular weight of the prepared
polycarbonate was 47,800 g/mol, in terms of PS standard. Further,
the results of NMR analysis confirmed that the repeating unit
derived from the compound (1) was included in an amount of 5 wt %,
based on the weight of the total repeating units.
Example 5
[0119] (1) Preparation of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate
##STR00017##
[0120] The same compound as in (1) of Example 1 was used.
[0121] (2) Preparation of Polycarbonate Resin
[0122] A polycarbonate was prepared in the same manner as in the
method of preparing a polycarbonate of Example 1, except that 30.43
g of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate of Example 1 and 107.8 g of bisphenol-A
were used. In this regard, a weight average molecular weight of the
prepared polycarbonate was 49,500 g/mol, in terms of PS standard.
Further, the results of NMR analysis confirmed that the repeating
unit derived from the compound (1) was included in an amount of 20
wt %, based on the weight of the total repeating units.
Example 6
[0123] (1) Preparation of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
thiophene-2,5-dicarboxylate
##STR00018##
[0124] The same compound as in (1) of Example 2 was used.
[0125] (2) Preparation of Polycarbonate Resin
[0126] A polycarbonate was prepared in the same manner as in the
method of preparing a polycarbonate of Example 1, except that 30.44
g of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
thiophene-2,5-dicarboxylate of Example 2 was used instead of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate of Example 1 and 107.96 g of bisphenol-A
was used. In this regard, a weight average molecular weight of the
prepared polycarbonate was 44,100 g/mol, in terms of PS standard.
Further, the results of NMR analysis confirmed that the repeating
unit derived from the compound (1) was included in an amount of 20
wt %, based on the weight of the total repeating units.
Example 7
[0127] (1) Preparation of
bis(3-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate
##STR00019##
[0128] Synthesis was performed in the same manner as in (1) of
Example 1, except that 3-hydroxybenzoic acid was used in an equal
amount, instead of 4-hydroxybenzoic acid of Example 1. The final
compound,
bis(3-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate (weight average molecular weight: 3,500
g/mol, n=5-6) was obtained in a final yield of 80%.
[0129] .sup.1H-NMR (DMSO-d.sub.6) of the compound is shown in FIG.
5.
[0130] (2) Preparation of Polycarbonate Resin
[0131] A polycarbonate was prepared in the same manner as in the
method of preparing a polycarbonate of Example 1, except that
bis(3-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate prepared in Example 1 was used instead of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate of Example 1. In this regard, a weight
average molecular weight of the prepared polycarbonate was 47,200
g/mol, in terms of PS standard. Further, the results of NMR
analysis confirmed that the repeating unit derived from the
compound (1) was included in an amount of 10 wt %, based on the
weight of the total repeating units.
[0132] .sup.1H-NMR (CDCl.sub.3-d.sub.1) of the compound is shown in
FIG. 6.
Example 8
[0133] (1) Preparation of
bis(3-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
thiophene-2,5-dicarboxylate
##STR00020##
[0134] Synthesis was performed in the same manner as in (1) of
Example 1, except that 3-hydroxybenzoic acid was used in an equal
amount, instead of 4-hydroxybenzoic acid of Example 1, and 8.82 g
of thiophene-2,5-dicarboxylic acid was used, instead of
2,5-Furandicarboxylic acid. The final compound,
bis(3-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
thiophene-2,5-dicarboxylate (weight average molecular weight: 4,700
g/mol, n=7-8) was obtained in a final yield of 79%.
[0135] .sup.1H-NMR (DMSO-d.sub.6) of the compound is shown in FIG.
7.
[0136] (2) Preparation of Polycarbonate Resin
[0137] A polycarbonate was prepared in the same manner as in the
method of preparing a polycarbonate of Example 1, except that 14.03
g of
bis(3-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
thiophene-2,5-dicarboxylate prepared in (1) was used instead of
bis(4-((4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)carbonyl)phenyl)
furan-2,5-dicarboxylate of Example 1, and 112.55 g of bisphenol-A
was used. In this regard, a weight average molecular weight of the
prepared polycarbonate was 47,400 g/mol, in terms of PS standard.
Further, the results of NMR analysis confirmed that the repeating
unit derived from the compound (1) was included in an amount of 10
wt %, based on the weight of the total repeating units.
[0138] .sup.1H-NMR (CDCl.sub.3-d.sub.1) of the compound is shown in
FIG. 8.
Comparative Example 1
[0139] 619 g of water, 116.5 g of bisphenol A, 102.5 g of 40% by
weight of NaOH, and 195 ml of MeCl.sub.2 were placed in a 2-L main
reactor equipped with a nitrogen purge device and a condenser and
enabling maintenance at room temperature using a circulator,
followed by stirring for several minutes.
[0140] Nitrogen purging was stopped, 62.81 g of triphosgene and 120
ml of MeCl.sub.2 were placed in a 1-L round bottom flask,
triphosgene was dissolved therein, and the dissolved triphosgene
solution was slowly added to the main reactor containing dissolved
BPA. After the addition was completed, 2.7 g of PTBP
(p-tert-butylphenol) was added and stirred for 10 min. After
stirring was completed, 99.4 g of 40% by weight of a NaOH aqueous
solution was added, and 1.04 g of TEA as a coupling agent was
added. At this time, reaction pH was maintained at 11 to 13. After
the reaction solution was allowed to stand for a time for
sufficient reaction, pH was decreased to 3-4 by addition of HCl to
complete the reaction. Then, stirring was stopped, the polymer
layer was separated from the aqueous layer, the aqueous layer was
removed, and the residue was washed with pure H.sub.2O again, and
this process was repeated a total of 3 to 5 times.
[0141] After the washing was completely carried out, only the
polymer layer was extracted, and polymer crystals were obtained by
re-precipitation using a non-solvent of methanol, H.sub.2O, etc. In
this regard, a weight average molecular weight of the prepared
polycarbonate was 46,000 g/mol, in terms of PS standard.
Experimental Example: Evaluation of Physical Properties of
Polycarbonate
[0142] Characteristics of injection specimens of the polycarbonates
prepared in Examples and Comparative Examples were measured by the
following methods, and the results are shown in Table 1. [0143]
Weight average molecular weight (g/mol): 200 mg of the polymer
resin was diluted with 200 ml of a tetrahydrofuran (THF) solvent to
prepare a sample of about 1000 ppm, of which molecular weight was
measured using an Agilent 1200 series GPC system through an RI
detector at a flow rate of 1 ml/min. To calculate the molecular
weight of the sample, eight PS standards were used to prepare a
calibration curve, and based on the curve, the molecular weight of
the sample was determined. [0144] Measurement of weather resistance
(.DELTA.E): L, a, and b values of a specimen having a thickness of
1/8 inch were measured in accordance with ASTM D7869 method, and
the corresponding specimen was left under 2250 hr weather
resistance condition in a Weather-Ometer.RTM. instrument, and then
L', a' and b' values were measured again. Weather resistance
.DELTA.E was calculated therefrom according to the following
Equation 1.
[0144] .DELTA.E= {square root over
(((L'-L).sup.2+(a'-a).sup.2+(b'-b).sup.2))} [Equation 1] [0145]
Measurement of pencil hardness: In accordance with ASTM D3363,
pencil was fixed at an angle of 45 degree in a pencil hardness
tester, and pencil hardness was measured with pencils of 2B, B, and
HB under a load of 1 kg. [0146] Transparency: In accordance with
ASTM D1003, transmittance was measured in the range of about 350 nm
to 1050 nm using UltraScan PRO (manufactured by HunterLab). [0147]
Yellow Index (YI): In accordance with ASTM D1925, YI value was
measured at room temperature (20.degree. C.) using a UltraScan PRO
(manufactured by HunterLab).
TABLE-US-00001 [0147] TABLE 1 Kind of repeating Weight unit of
average Chemical molecular Weather Trans- Formula 1/ weight
resistance Pencil parency Weight ratio (g/mol) (.DELTA.E) hardness
(%) YI Example 1 Chemical 48,000 6.9 B 89.1 2.8 Formula 1-1
(X.dbd.O), 10 wt % Example 2 Chemical 46,400 6.9 B 89.2 3.3 Formula
1-1 (X.dbd.S), 10 wt % Example 3 Chemical 45,200 7.4 B 89.1 2.6
Formula 1-1 (X.dbd.O), 5 wt % Example 4 Chemical 47,800 7.6 B 89.3
2.8 Formula 1-1 (X.dbd.S), 5 wt % Example 5 Chemical 49,500 4.7 HB
89.2 3.0 Formula 1-1 (X.dbd.O), 20 wt % Example 6 Chemical 44,100
5.2 HB 88.9 3.5 Formula 1-1 (X.dbd.S), 20 wt % Example 7 Chemical
47,200 6.3 HB 89.2 3.1 Formula 1-2 (X.dbd.O), 10 wt % Example 8
Chemical 47,400 6.6 B 89.0 3.4 Formula 1-2 (X.dbd.S), 10 wt %
Comparative 100% BPA 46,000 12 2B 89.9 2.0 Example 1 PC
[0148] Referring to Table 1, the polycarbonates of all Examples
including the repeating units of the present invention showed the
effects of having remarkably improved weather resistance and pencil
hardness while having similar transparency and yellow index, as
compared with the general BPA polycarbonate of Comparative Example
1.
* * * * *